The Journal of Organic Chemistry
Note
5-Iodo-6-(4-methoxyphenyl)-11-methyl-11H-benzo[a]-
carbazole (2d): yield 42 mg, 90%; colorless solid; Rf = 0.22 (20:1
Hex/EtOAc); H NMR (300 MHz, CDCl3) δ 3.98 (s, 3H), 4.44 (s,
6-(4-Bromophenyl)-5-iodo-11-methyl-11H-benzo[a]-
carbazole (2j): yield 25 mg, 54%; colorless solid; Rf = 0.29 (20:1
Hex/EtOAc); 1H NMR (300 MHz, CDCl3) δ 4.43 (s, 3H), 6.55 (d, J
= 8.1 Hz, 1H), 7.01 (t, J = 7.2 Hz, 1H), 7.27−7.24 (m, 2H), 7.43 (td, J
= 6.9, 0.9 Hz, 1H), 7.53 (d, J = 8.1 Hz, 1H), 7.67−7.63 (m, 2H),
7.76−7.67 (m, 2H), 8.61−8.58 (m, 1H), 8,78−8.74 (m, 1H); 13C
NMR (100 MHz, CDCl3) δ 34.5, 96.0, 109.0, 118.5, 119.9, 121.8,
122.2, 122.2, 122.4, 122.6, 125.1, 125.9, 126.7, 131.2, 132.1, 133.1,
134.8, 136.0, 140.8, 140.9, 144.3; mp 188−190 °C; MS (70 eV) m/z
469 (35) [M + 2], 467 (100) [M+], 109 (28), 93 (28); HRMS (ESI-
TOF) calcd for C23H15BrIN 510.9433, found 510.9435; IR (KBr,
cm−1) 3057, 2927, 1607, 1489.
1
3H), 6.58 (d, J = 7.8 Hz, 1H), 6.99 (t, J = 7.5 Hz, 1H), 7.14 (d, J = 8.7
Hz, 2H), 7.29 (d, J = 8.7 Hz, 2H), 7.41 (t, J = 7.2 Hz, 1H), 7.52 (d, J =
8.4 Hz, 1H), 7.67−7.64 (m, 2H), 8.64−8.61 (m, 1H), 8.77−8.72 (m,
1H); 13C NMR (100 MHz, CDCl3) δ 34.5, 55.3, 108.8, 114.1, 114.2,
119.3, 119.7, 122.1, 122.4, 122.6, 122.7, 124.9, 125.7, 126.5, 130.5,
133.2, 134.0, 134.9, 138.1, 140.9, 141.9, 159.3; mp 158−160 °C; MS
(70 eV) m/z 463 (100) [M+], 335 (15), 292 (19); HRMS (ESI-TOF)
calcd for C24H18INO 463.0433, found 463.0431; IR (KBr, cm−1) 3052,
2936, 1609, 1506, 1263.
5-Iodo-11-methyl-6-(4-(trifluoromethyl)phenyl)-11H-benzo-
[a]carbazole (2k): yield 47 mg, 93%; colorless solid; Rf = 0.32 (20:1
Hex/EtOAc); 1H NMR (400 MHz, CDCl3) δ 4.41 (s, 3H), 6.39 (d, J
= 8.0 Hz, 1H), 6.97 (td, J = 8.0, 0.8 Hz, 1H), 7.42 (td, J = 8.0, 0.8 Hz,
1H), 7.48−7.53 (m, 3H), 7.64−7.70 (m, 2H), 7.87 (dd, J = 8.0, 0.8
Hz, 2H), 8.58−8.61 (m, 1H), 8.71−8.74 (m, 1H); 13C NMR (100
MHz, CDCl3) δ 34.5, 95.4, 109.1, 118.4, 119.9, 121.5, 122.1, 122.5,
122.7, 125.1, 125.8, 125.9, 125.9, 125.9, 126.1, 126.8, 130.0, 133.0,
134.8, 136.1, 140.5, 140.9, 148.9; mp 172−174 °C; MS (70 eV) m/z
501 (100) [M+], 373 (23); HRMS (ESI-TOF) calcd for C24H15F3IN
501.0201, found 501.0200; IR (KBr, cm−1) 3052, 2929, 1616, 1508.
5-Iodo-11-methyl-6-(4-nitrophenyl)-11H-benzo[a]carbazole
(2l): yield 46 mg, 95%; pale yellow solid; Rf = 0.12 (20:1 Hex/
EtOAc); 1H NMR (400 MHz, CDCl3) δ 4.46 (s, 3H), 6.41 (d, J = 8.0
Hz, 1H), 6.99 (td, J = 7.2, 1.2 Hz, 1H), 7.44 (td, J = 6.8, 1.2 Hz, 1H),
7.55−7.60 (m, 3H), 7.68−7.74 (m, 2H), 8.48−8.52 (m, 2H), 8.59−
8.61 (m, 1H), 8.76−8.78 (m, 1H); 13C NMR (100 MHz, CDCl3) δ
34.6, 94.8, 109.2. 118.0, 120.0, 121.3, 121.8, 122.5, 122.8, 124.3, 125.3,
126.4, 127.0, 130.9, 132.9, 134.8, 136.2, 139.7, 141.0, 147.7, 151.9; mp
218−220 °C; MS (70 eV) m/z (%): 487 (100) [M+], 290 (17);
HRMS (ESI-TOF) calcd for C23H15IN2O2 478.0178, found 478.0179;
IR (KBr, cm−1) 3054, 2927, 1601, 1523, 1348.
5-Iodo-11-methyl-6-p-tolyl-11H-benzo[a]carbazole (2e):
yield 43 mg, 95%; colorless solid; Rf = 0.36 (20:1 Hex/EtOAc); H
1
NMR (400 MHz, CDCl3) δ 2.56 (s, 3H), 4.41 (s, 3H), 6.51 (d, J = 8.4
Hz, 1H), 6.97 (td, J = 8.0, 1.2 Hz, 1H), 7.24−7.26 (m, 2H), 7.38−7.43
(m, 3H), 7.50 (d, J = 8.8 Hz, 1H), 7.62−7.66 (m, 2H), 8.60−8.62 (m,
1H), 8.70−8.73 (m, 1H); 13C NMR (100 MHz, CDCl3) δ 21.6, 34.5,
96.5, 108.8, 119.1, 119.7, 122.1, 122.4, 122.5, 122.6, 124.9, 125.6,
126.5, 129.1, 129.5, 133.2, 134.8, 135.9, 137.7, 140.9, 142.2, 142.6; mp
170−172 °C; MS (70 eV) m/z 447 (100) [M+], 319 (20), 305 (18);
HRMS (ESI-TOF) calcd for C24H18IN 447.0484, found 447.0482; IR
(KBr, cm−1) 3053, 2925, 1608, 1507.
5-Iodo-11-methyl-6-m-tolyl-11H-benzo[a]carbazole (2f):
1
yield 38 mg, 85%; colorless solid; Rf = 0.36 (20:1 Hex/EtOAc); H
NMR (400 MHz, CDCl3) δ 2.47 (s, 3H), 4.42 (s, 3H), 6.47 (d, J = 8.0
Hz, 1H), 6.96 (td, J = 8.0, 0.8 Hz, 1H), 7.18 (d, J = 8.4 Hz, 1H), 7.19
(s, 1H), 7.38−7.42 (m, 2H), 7.50 (t, J = 7.2 Hz, 2H), 7.64−7.66 (m,
2H), 8.61−8.63 (m, 1H), 8.72−8.74 (m, 1H); 13C NMR (100 MHz,
CDCl3) δ 21.6, 34.5, 96.0, 108.8, 119.0, 119.7, 122.1, 122.4, 122.5,
122.6, 124.9, 125.7, 126.3, 126.5, 128.7, 128.7, 129.9, 133.2, 134.8,
135.9, 138.4, 141.0, 142.3, 145.3; mp 144−146 °C; MS (70 eV) m/z
447 (100) [M+], 305 (12); HRMS (ESI-TOF) calcd for C24H18IN
447.0484, found 447.0484. IR (KBr, cm−1) 3048, 2926, 1606, 1514.
5-Iodo-11-methyl-6-o-tolyl-11H-benzo[a]carbazole (2g):
5-Iodo-8,10,11-trimethyl-6-propyl-11H-benzo[a]carbazole
(2m): yield 41 mg, 79%; brown solid; Rf = 0.52 (20:1 Hex/EtOAc);
1H NMR (300 MHz, CDCl3) δ 1.26 (t, J = 7.2 Hz, 3H), 1.84 (x, J =
1
yield 38 mg, 85%; colorless solid; Rf = 0.34 (20:1 Hex/EtOAc); H
NMR (400 MHz, CDCl3) δ 1.98 (s, 3H), 4.45 (s, 3H), 6.40 (dd, J =
8.0, 0.8 Hz, 1H), 6.96 (td, J = 8.0, 0.8 Hz, 1H), 7.22 (d, J = 7.2 Hz,
1H), 7.39−7.46 (m, 3H), 7.51 (t, J = 7.6 Hz, 2H), 7.66−7.68 (m, 2H),
8.61−8.63 (m, 1H), 8.75−8.77 (m, 1H); 13C NMR (100 MHz,
CDCl3) δ 19.6, 34.5, 96.1, 108.8, 118.6, 120.0, 121.5, 122.5, 122.6,
122.6, 124.9, 125.7, 126.5, 126.5, 128.4, 129.3, 130.3, 133.3, 134.6,
136.1, 136.1, 140.9, 141.7, 144.6; mp 156−158 °C; MS (70 eV) m/z
447 (100) [M+], 320 (29), 305 (50); HRMS (ESI-TOF) calcd for
C24H18IN 447.0484, found 447.0487. IR (KBr, cm−1) 3053, 2925,
1607, 1508.
7.5 Hz, 2H), 2.53 (s, 3H), 2.84 (s, 3H), 3.62−3.56 (m, 2H), 4.30 (s,
3H), 7.08 (s, 1H), 7.60−7.51 (m, 2H), 7.74 (s, 1H), 8.35 (dd, J = 7.2,
2.1 Hz, 1H), 8.53 (dd, J = 7.5, 1.8 Hz, 1H); 13C NMR (100 MHz,
CDCl3) δ 14.3, 20.6, 21.7, 22.0, 39.0, 42.5, 97.9, 119.0, 120.0, 121.4,
121.7, 123.2, 124.4, 124.6, 126.2, 129.5, 129.9, 133.6, 134.4, 140.1,
140.8, 141.5; mp 98−100 °C; MS (70 eV) m/z 427 (100) [M+], 308
(51), 281 (92), 272 (60); HRMS (ESI-TOF) calcd for C22H22IN
427.0797, found 427.0795; IR (KBr, cm−1): 3051, 2957, 2926, 2870,
1604, 1469.
5-Iodo-8,10,11-trimethyl-6-phenyl-11H-benzo[a]carbazole
5-Iodo-11-methyl-6-phenyl-11H-benzo[a]carbazole (2h):
(2n): yield 39 mg, 84%; pale yellow solid; Rf = 0.55 (20:1 Hex/
1
1
yield 39 mg, 90%; colorless solid; Rf = 0.30 (20:1 Hex/EtOAc); H
EtOAc); H NMR (400 MHz, CDCl3) δ 2.15 (s, 3H), 2.83 (s, 3H),
NMR (400 MHz, CDCl3) δ 4.44 (s, 3H), 6.44 (dd, J = 8.0, 1.2 Hz,
1H), 6.95 (td, J = 8.0, 1.2 Hz, 1H), 7.37−7.42 (m, 3H), 7.52 (d, J =
8.4 Hz, 1H), 7.60−7.67 (m, 5H), 8.61−8.64 (m, 1H), 8.73−8.76 (m,
1H); 13C NMR (100 MHz, CDCl3) δ 34.5, 96.1, 108.9, 119.0, 119.7,
122.0, 122.4, 122.6, 122.6, 124.9, 125.7, 126.6, 128.1, 128.8, 129.4,
133.2, 134.9, 136.0, 141.0, 142.2, 145.5; mp 60−63 °C; MS (70 eV)
m/z 433 (100) [M+], 307 (32), 291 (31), 149 (39), 61 (31); HRMS
(ESI-TOF) calcd for C23H16IN 433.0327, found 433.0327. IR (KBr,
cm−1) 3053, 2927, 1605, 1507.
4.43 (s, 3H), 6.00 (s, 1H), 6.95 (s, 1H), 7.34−7.37 (m, 2H), 7.57−
7.67 (m, 5H), 8.49−8.53 (m, 1H), 8.56−8.61 (m, 1H); 13C NMR
(100 MHz, CDCl3) δ 20.0, 21.2, 38.7, 96.4, 119.8, 120.9, 122.4, 123.2,
124.5, 125.4, 126.5, 127.9, 128.2, 128.3, 128.5, 128.7, 129.4, 129.5,
129.5, 129.7, 131.5, 133.2, 134.7, 136.9, 145.5; mp 110−112 °C; MS
(70 eV) m/z 461 (41) [M+], 335 (55), 149 (82), 61 (100); HRMS
(ESI-TOF) calcd for C25H20IN 461.0640, found 461.0639; IR (KBr,
cm−1) 3053, 2926, 2855, 1604, 1462.
Methyl 5-iodo-11-methyl-6-propyl-11H-benzo[a]carbazole-
8-carboxylate (2o): yield 31 mg, 67%; colorless solid; Rf = 0.43 (5:1
Hex/EtOAc); 1H NMR (400 MHz, CDCl3) δ 1.32 (t, J = 7.2 Hz, 3H),
1.80−1.90 (m, 2H), 3.59−3.63 (m, 2H), 4.00 (s, 3H), 4.33 (s, 3H),
7.52 (d, J = 8.8, 1H), 7.54−7.63 (m, 2H), 8.19 (dd, J = 8.8, 1.6 Hz,
1H), 8.55−8.58 (m, 2H), 8.87 (d, J = 1.6 Hz, 1H); 13C NMR (100
MHz, CDCl3) δ 14.2, 21.8, 34.8, 42.7, 52.0, 98.5, 108.8, 118.2, 121.8,
121.8, 122.2, 124.9, 125.3, 126.0, 126.7, 133.7, 134.7, 137.1, 140.9,
143.4, 167.8; mp 188−190 °C; MS (70 eV) m/z 457 (100) [M+], 302
(53); HRMS (ESI-TOF) calcd for C22H20INO2 457.0539, found
457.0541; IR (KBr, cm−1) 3052, 2955, 1710, 1610, 1429.
6-(4-Chlorophenyl)-5-iodo-11-methyl-11H-benzo[a]-
carbazole (2i): yield 33 mg, 70%; colorless solid; Rf = 0.30 (20:1
Hex/EtOAc); 1H NMR (400 MHz, CDCl3) δ 4.44 (s, 3H), 6.54 (dd, J
= 8.0, 1.2 Hz, 1H), 7.01 (td, J = 8.0, 1.2 Hz, 1H), 7.31−7.34 (m, 2H),
7.43 (td, J = 8.0, 1.2 Hz, 1H), 7.54 (d, J = 8.0 Hz, 1H), 7.58−7.62 (m,
2H), 7.65−7.70 (m, 2H), 8.60−8.62 (m, 1H), 8.74−8.76 (m, 1H); 13
C
NMR (100 MHz, CDCl3) δ 34.5, 96.1, 109.0, 118.7, 119.9, 121.8,
122.3, 122.5, 122.7, 125.1, 126.0, 126.7, 129.2, 130.9, 133.1, 134.0,
134.9, 136.1, 140.8, 141.0, 143.8; mp 177−180 °C; MS (70 eV) m/z
469 (35) [M + 2], 467 (100) [M+], 109 (28), 93 (28); HRMS (ESI-
TOF) calcd for C23H15ClIN 466.9938, found 466.9935. IR (KBr,
cm−1) 3054, 2927, 1606, 1491.
Methyl 5-iodo-11-methyl-6-phenyl-11H-benzo[a]carbazole-
8-carboxylate (2p): yield 37 mg, 75%; colorless solid; Rf = 0.40 (5:1
10272
dx.doi.org/10.1021/jo201795t|J. Org. Chem. 2011, 76, 10269−10274